Aniline derivatives and process for producing the same

ABSTRACT

Disclosed herein is a process for producing a sulfoneamide represented by the following formula (6) as an intermediate of a 6-haloalkyl-3-phenyluracil derivative, from as a starting material 4-halogeno-3-nitroaniline (9) or 2-halogeno-5-nitroaniline (10): ##STR1## (wherein X and Y independently represent a halogen atom, R represents a C 1  -C 4  alkyl group or a C 1  -C 3  haloalkyl group and R&#39; represents a C 1  -C 4  alkyl group or a phenyl group).

This application is a division of application Ser. No. 07/823,539, filedon Jan. 21, 1992, now abandoned.

BACKGROUND OF THE INVENTION

The present invention relates to a novel intermediate used for producinga 6-haloalkyl-3-phenyluracil derivative [described in Japanese PatentApplication Nos. Hei 2-400475 (1990) and Hei 3-314391 (1991)] which isuseful as a herbicide and a process for producing the same.

As aniline derivatives, N-(3-amino-4-chlorophenyl)methanesulfonamide isdescribed in West German Patent Nos 2938633 and 3124172, methyl5-amino-2-chlorocarbanilate is described in West German Patent No.2703838, methyl 2-chloro-5-nitrocarbanilate is described in U.S. Pat.No. 2,860,166 and West German Patent Nos. 2703838, 2725146, 2846625 and2926049, ethyl 5-amino-2-chlorocarbanilate is described in U.S. Pat. No.3,920,444, ethyl 2-chloro-5-nitrocarbanilate is described in JustusLiebigs Ann. Chem. vol 721. p.14,N-(4-fluoro-3-nitrophenyl)methanesulfonamide is described in U.S. Pat.No. 4,507,479, a methyl ester and a phenyl ester of2-fluoro-5-nitrocarbanilic acid are discribed in U.S. Pat. No.4,226,613, and a methyl ester and a phenyl ester of5-amino-2-fluorocarbanilic acid (since they are not isolated, thephysical properties are not described) are described in U.S. Pat. No.4,227,007.

These literatures only describe these derivatives as an intermediate ora byproduct, and a process for producing these derivatives are notalways satisfactory. Provision of a more advantageous process thereofis, therefore, demanded.

In addition, no benzene derivative having both functional groups ofcarbonate and sulfoneamide and substituted by one or two halogen atom isknown at all.

As a result of earnest investigations of a process for producing a6-haloalkyl-3-phenyluracil derivative [described in Japanese PatentApplication Nos. Hei 2-400475 (1990) and Hei 3-314391 (1991)] which isuseful as a herbicide, it has been found that an intermediate producedin accordance with the-following scheme is useful as an intermediate forproducing the 6-haloalkyl-3-phenyluracil derivative: ##STR2## (whereinX, Y and Hal independently represent a halogen atom, R represents a C₁-C₄ alkyl group or a C₁ -C₃ haloalkyl group, and R' represents a C₁ -C₄alkyl group or a phenyl group). The present invention has been achievedon the basis of this finding.

SUMMARY OF THE INVENTION

In a first aspect of the present invention, there is provided a processfor producing a sulfoneamide derivative represented by the followingformula (6): ##STR3## (wherein X and Y independently represent a halogenatom, R represents a C₁ -C₄ alkyl group or a C₁ -C₃ haloalkyl group andR' represents a C₁ -C₄ alkyl group or a phenyl group), comprising thesteps of:

reacting 4-halogeno-3-nitroaniline represented by the following generalformula (9): ##STR4## with an alkylsulfonyl halide represented by thefollowing general formula (11):

    Hal--SO.sub.2 R                                            (11)

(wherein Hal represents a halogen atom),

so as to obtain a nitroaniline derivative represented by the followinggeneral formula (1): ##STR5## reducing the nitroaniline derivativerepresented by the formula (1) so as to obtain a diamine derivativerepresented by the following general formula (2): ##STR6## reacting thediamine derivative represented by the formula (2) with a halogenoformaterepresented by the following general formula (12):

    Hal--CO.sub.2 R'                                           (12)

so as to obtain an anilide derivative represented by the followinggeneral formula (5): ##STR7## halogenating the anilide derivativerepresented by the formula (5).

In a second aspect of the present invention, there is provided a processfor producing a sulfonamide derivative represented by the followingformula (6): ##STR8## (wherein X and Y independently represent a halogenatom, R represents a C₁ -C₄ alkyl group or a C₁ -C₃ haloalkyl group andR' represents a C₁ -C₄ alkyl group or a phenyl group), comprising thesteps of:

reacting 2-halogeno-5-nitroaniline represented by the following generalformula (10): ##STR9## with a halogenoformate represented by thefollowing general formula (12):

    Hal--CO.sub.2 R'                                           (12)

(wherein Hal represents a halogen atom)

so as to obtain a nitrocarbanilide derivative represented by thefollowing general formula (3): ##STR10## reducing the nitrocarbanilidederivative represented by the formula (3) so as to obtain anaminocarbanilide derivative represented by the following general formula(4): ##STR11## reacting the aminocarbanilide derivative represented bythe general formula (4) with an alkylsulfonyl halide represented by thefollowing general formula (11):

    Hal--SO.sub.2 R                                            (11)

so as to obtain an anilide derivative represented by the followinggeneral formula (5): ##STR12## halogenating the anilide derivativerepresented by the formula (5).

In a third aspect of the present invention, there is provided a processfor producing a nitroaniline derivative represented by the followingformula (1): ##STR13## (wherein X represents a halogen atom and Rrepresents a C₁ -C₄ alkyl group or a C₁ -C₃ haloalkyl group), comprisingthe step of reacting 4-halogeno-3-nitroaniline represented by thefollowing general formula (9): ##STR14## with an alkylsulfonyl haliderepresented by the following general formula (11):

    Hal--SO.sub.2 R                                            (11)

(wherein Hal represents a halogen atom).

In a fourth aspect of the present invention, there is provided a processfor producing a diamine derivative represented by the following formula(2): ##STR15## (wherein X represents a halogen atom and R represents aC₁ -C₄ alkyl group or a C₁ -C₃ haloalkyl group), comprising the step ofreducing a nitroaniline derivative represented by the following generalformula (1): ##STR16##

In a fifth aspect of the present invention, there is provided a processfor producing an anilide derivative represented by the following generalformula (5): ##STR17## (wherein X represents a halogen atom, Rrepresents a C₁ -C₄ alkyl group or a C₁ -C₃ haloalkyl group and R'represents a C₁ -C₄ alkyl group or a phenyl group), comprising the stepof reacting a diamine derivative represented by the following formula(2): ##STR18## with a halogenoformate represented by the followinggeneral formula (12):

    Hal--CO.sub.2 R'                                           (12)

(wherein Hal represents a halogen atom).

In a sixth aspect of the present invention, there is provided a processfor producing a nitrocarbanilide derivative represented by the followinggeneral formula (3): ##STR19## (wherein X represents a halogen atom andR' represents a C₁ -C₄ alkyl group or a phenyl group) comprising thestep of reacting 2-halogeno-5-nitroaniline represented by the followinggeneral formula (10): ##STR20## with a halogenoformate represented bythe following general formula (12):

    Hal--CO.sub.2 R'                                           (12)

(wherein Hal represents a halogen atom).

In a seventh aspect of the present invention, there is provided aprocess for producing an aminocarbanilide derivative represented by thefollowing general formula (4): ##STR21## (wherein X represents a halogenatom and R' represents a C₁ -C₄ alkyl group or a phenyl group)comprising the step of reducing a nitrocarbanilide derivativerepresented by the following general formula (3): ##STR22##

8. In an eighth aspect of the present invention, there is provided aprocess for producing an anilide derivative represented by the followinggeneral formula (5): ##STR23## (wherein X represents a halogen atom, Rrepresents a C₁ -C₄ alkyl group or a C₁ -C₃ haloalkyl group and R'represents a C₁ -C₄ alkyl group or a phenyl group), comprising the stepof reacting an aminocarbanilide derivative represented by the followinggeneral formula (4): ##STR24## with an alkylsulfonyl halide representedby the following general formula (11):

    Hal--SO.sub.2 R                                            (11)

(wherein Hal represents a halogen atom).

In a ninth aspect of the present invention, there is provided a processfor producing a sulfonamide derivative represented by the followingformula (6): ##STR25## (wherein X and Y independently represent ahalogen atom, R represents a C₁ -C₄ alkyl group or a C₁ -C₃ haloalkylgroup and R' represents a C₁ -C₄ alkyl group or a phenyl group),comprising the step of halogenating an anilide derivative represented bythe following general formula (5): ##STR26##

In a tenth aspect of the present invention, there is provided anitroaniline derivative are represented by the following general formula(1): ##STR27## wherein X represents a halogen atom and R represents a C₁-C₄ alkyl group or a C₁ -C₃ haloalkyl group, provided that when X is afluorine atom, R is not a methyl group.

In an eleventh of the present invention, there is provided a diaminederivative represented by the following formula (2): ##STR28## wherein Xrepresents a halogen atom, R represents a C₁ -C₄ alkyl group or a C₁ -C₃haloalkyl group, provided that when X is a chlorine atom, R is not amethyl group.

In a twelfth aspect of the present invention there is provided anitrocarbanilide derivative represented by the following general formula(3): ##STR29## wherein X represents a halogen atom and R' represents aC₁ -C₄ alkyl group or a phenyl group, provided that when X is a fluorineatom or a chlorine atom, R' is not a methyl group, when X is a fluorineatom, R' is not a phenyl group, and when X is a chlorine atom, R' is notan ethyl group.

In a thirteenth aspect of the present invention there is provided anaminocarbanilide derivative represented by the following general formula(4): ##STR30## wherein X represents a halogen atom and R' represents aC₁ -C₄ alkyl group or a phenyl group, provided that when X is a fluorineatom or a chlorine atom, R' is not a methyl group, when X is a fluorineatom, R' is not a phenyl group, and when X is a chlorine atom, R' is notan ethyl group.

In a fourteenth aspect of the present invention, there is provided ananilide derivative represented by the following general formula (5):##STR31## wherein X represents a halogen atom, R represents a C₁ -C₄alkyl group or a C₁ -C₃ haloalkyl group and R' represents a C₁ -C₄ alkylgroup or a phenyl group).

In a fifteenth aspect of the present invention, there is provided asulfonamide derivative represented by the following formula (6):##STR32## wherein X and Y independently represent a halogen atom, Rrepresents a C₁ -C₄ alkyl group or a C₁ -C₃ haloalkyl group and R'represents a C₁ -C₄ alkyl group or a phenyl group.

DETAILED DESCRIPTION OF THE INVENTION

In the above-described scheme, route 1 shows the process of producing acompound (5) with a high yield by subjecting a nitroaniline derivative(9) to sulfoneamidation, reducing the thus-obtained sulfoneamidederivative and carbamating the reduced product. Route 2 shows theprocess of producing a compound (5) with a high yield by carbamating anitroaniline derivative (10), reducing the carbamated derivative andsubjecting the reduced product to sulfoneamidation, and a process ofproducing a compound (6) with a high yield by halogenating thethus-obtained compound (5) positionally selectively.

These steps may be carried out either sequentially or continuously byappropriately selecting the conditions. A compound (8) can bemanufactured from the thus-obtained compound (6) [described in JapanesePatent Application Nos. Hei 2-400475 (1990) and Hei 3-314391 (1991)] bythe route in the following route. ##STR33## (wherein X, Y, R and R'represents the same as defined above, and R" represents a C₁ -C₆ alkylgroup, a phenyl group or a benzyl group).

The respective steps in the scheme will be explained in detail in thefollowing.

(A): Production of a compound (1) from the compound (9)

Ordinarily, the compound (11) of 0.5 to 3.0 mol, preferably 0.8 to 1.5mol based on the compound (9) is used. A base of 0.5 to 10 mol,preferably 0.8 to 5.0 mol based on the compound (9) is used. The basemay be used as a solvent.

As the base, nitrogen-containing organic bases such as pyridine,triethylamine, N,N-dimethylaniline, N,N-diethylaniline,4-(N,N-dimethylamino)pyridine and 1,4-diazabicyclo[2.2.2]octane, andinorganic bases such as sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate and sodium hydrogencarbonate are usable.

A solvent is ordinarily necessary for the reaction. As the solvent,aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleumether; aromatic hydrocarbons such as benzene, toluene, xylene andchlorobenzene; halogenated hydrocarbons such as chloroform and methylenechloride; ethers such as diethyl ether, dioxane and tetrahydrofuran;ketones such as acetone and methyl ethyl ketone; nitriles such asacetonitrile and isobutylonitrile; tertiary amines such as pyridine andN,N-diethylaniline; acid amides such as N,N-dimethylacetamide,N,N-dimethylformamide and N-methylpyrrolidone; sulfur-containingcompounds such as dimethylsulfoxide and sulfolane; and a mixture thereofmay be exemplified. Among these, the aromatic hydrocarbons, halogenarealhydrocarbons, tertiary amines and a mixture thereof are preferable.

The reaction temperature is ordinarily -10° to 180° C., preferably 0° C.to a reflux temperature.

The reaction time is ordinarily 1 to 72 hours, preferably 2 to 48 hours.

(B): Production of a compound (2) from the compound (1)

For reduction, a reagent reduction and catalytic hydrogenation may beadopted.

(Reagent reduction)

Ordinarily, a reducing agent of 1 to 20 mol, preferably 2 to 10 molbased on the compound (1) is used.

As the reducing agent, metals and metal salts such as zinc, aluminum,tin, stannous chloride and iron will be cited.

The reaction ordinarily requires a solvent. As the solvent, organicacids such as formic acid and acetic acid; inorganic acids such ashydrochloric acid, hydrobromic acid and sulfuric acid; esters such asethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; ethers such as tetrahydrofuran and dioxane; alcohols suchas methanol and ethanol; water; and a mixture thereof may beexemplified.

The reaction temperature is ordinarily 0° to 150° C., preferably 40° C.to a reflux temperature.

The reaction time is ordinarily 15 minutes to 24 hours, preferably 0.5to 8 hours.

(Catalytic hydrogenation)

Ordinarily, hydrogen of 2.8 to 3.2 mol, preferably 2.9 to 3.1 mol basedon the compound (1) is used. A catalyst of 0.001 to 10 wt %, preferably0.005 to 5 wt % based on the compound (1) is used.

As examples of the catalyst, platinum catalysts such as platinum oxide(IV), platinum black, platinum carbon powder, and platinum carbonsulfide powder; palladium catalysts such as palladium carbon powder,palladium alumina powder, palladium black and palladium oxide; osmiumcatalysts such as osmium carbon powder; rhenium catalysts such asrhenium carbon powder; and nickel catalysts such as Raney nickel will becited.

It is possible to add an inorganic acid such as sulfuric acid,hydrochloric acid, phosphoric acid and perchloric acid, and a base suchas pyridine and triethylamine in order to accelerate the reaction.

The reaction ordinarily requires a solvent. As the solvent, organicacids such as formic acid and acetic acid; esters such as ethyl acetateand butyl acetate; ethers such as diethyl ether, tetrahydrofuran anddioxane; alcohols such as methanol and ethanol; aliphatic hydrocarbonssuch as cyclohexane and heptane; aromatic hydrocarbons such as benzeneand toluene; acid amides such as N,N-dimethylformamide; water; and amixture thereof may be exemplified. Among these, the organic acides,ethers, alcohols, aliphatic hydrocarbons, water and a mixture thereofare preferable.

The reaction temperature is ordinarily 0° to 200° C., preferably 25° to150° C.

The reaction time is ordinarily 0.5 to 24 hours, preferably 1 to 12hours.

The reaction pressure is ordinarily 0 to 200 atm, preferably 0 to 100atm (Gauge).

(C) Production of the compound (5) from a compound (2)

Ordinarily, a compound (12) of 0.5 to 2.0 mol, preferably 0.8 to 1.2 molbased on the compound (2) is used.

Ordinarily, a base of 0.5 to 2.0 mol, preferably 0.8 to 1.5 mol based onthe compound (2) is used. The base may be used as a solvent.

As the base, nitrogen-containing organic bases such as pyridine,triethylamine, N,N-dimethylaniline, N,N-diethylaniline,4-(N,N-dimethylamino)pyridine and 1,4-diazabicyclo[2.2.2]octane andinorganic bases such as sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate and sodium hydrogencarbonate are usable.

A solvent is ordinarily necessary for the reaction. As the solvent,aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleumether; aromatic hydrocarbons such as benzene, toluene, xylene andchlorobenzene; halogenated hydrocarbons such as chloroform and methylenechloride; ethers such as diethyl ether, dioxane and tetrahydrofuran;ketones such as acetone and methyl ethyl ketone; nitriles such asacetonitrile and isobutylonitrile; tertiary amines such as pyridine andN,N-diethylaniline; acid amides such as N,N-dimethylacetamide,N,N-dimethylformamide and N-methylpyrrolidone; sulfur-containingcompounds such as dimethylsulfoxide and sulfolane; and a mixture thereofmay be exemplified. Among these, the aromatic hydrocarbons, halogenatedhydrocarbons, ketones, nitriles, tertiary amines and a mixture thereofare preferable.

The reaction temperatrure is ordinarily -10° C. to a reflux temperature.

The reaction time is ordinarily 0.5 to 72 hours, preferably 1 to 12hours.

(D) Production of a compound (3) from a compound (10)

Ordinarily, a compound (12) of 0.5 to 2.0 mol, preferably 0.8 to 1.5 molbased on the compound (10) is used.

Ordinarily, a base of 0.5 to 2.0 mol, preferably 0.8 to 1.6 mol based onthe compound (10) is used. The base may be used as a solvent.

As the base, nitrogen-containing organic bases such as pyridine,triethylamine, N,N-dimethylaniline, N,N-diethylaniline,4-(N,N-dimethylamino)pyridine and 1,4-diazabicyclo[2.2.2]octane andinorganic bases such as sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate and sodium hydrogencarbonate are usable.

A solvent is ordinarily necessary for the reaction. As the solvent,aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleumether; aromatic hydrocarbons such as benzene, toluene, xylene andchlorobenzene; halogenated hydrocarbons such as chloroform and methylenechloride; ethers such as diethyl ether, dioxane and tetrahydrofuran;ketones such as acetone and methyl ethyl ketone; nitriles such asacetonitrile and isobutylonitrile; tertiary amines such as pyridine andN,N-diethylaniline; acid amides such as N,N-dimethylacetamide,N,N-dimethylformamide and N-methylpyrrolidone; sulfur-containingcompounds such as dimethylsulfoxide and sulfolane; and a mixture thereofmay be exemplified. Among these, the aromatic hydrocarbons, halogenatedhydrocarbons, ketones, nitriles, tertiary amines and a mixture thereofare preferable.

The reaction temperature is ordinarily -10° C. to a reflux temperature.

The reaction time is ordinarily 0.5 to 72 hours, preferably 1 to 48hours.

(E) Production of a compound (4) from the compound (3)

The reaction is carried out under the same conditions as those in (B):Production of a compound (2) from the compound (1).

(F) Production of the compound (5) from the compound (4)

Ordinarily, a compound (11) of 0.5 to 3.0 mol, preferably 0.8 to 1.5 molbased on the compound (4) is used.

Ordinarily, a base of 0.5 to 10 mol, preferably 0.8 to 5.0 mol based onthe compound (4) is used. The base may be used as a solvent.

As the base, nitrogen-containing organic bases such as pyridine,triethylamine, N,N-dimethylaniline, N,N-diethylaniline,4-(N,N-dimethylamino)pyridine and 1,4-diazabicyclo[2.2.2]octane, andinorganic bases such as sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate and sodium hydrogencarbonate are usable.

A solvent is ordinarily necessary for the reaction. As the solvent,aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleumether; aromatic hydrocarbons such as benzene, toluene, xylene andchlorobenzene; halogenated hydrocarbons such as chloroform and methylenechloride; ethers such as diethyl ether, dioxane and tetrahydrofuran;ketones such as acetone and methyl ethyl ketone; nitriles such asacetonitrile and isobutylonitrile; tertiary amines such as pyridine andN,N-diethylaniline; acid amides such as N,N-dimethylacetamide,N,N-dimethylformamide and N-methylpyrrolidone; sulfur-containingcompounds such as dimethylsulfoxide and sulfolane; and a mixture thereofmay be exemplified. Among these, the aromatic hydrocarbons, halogenatedhydrocarbons, tertiary amines and a mixture thereof are preferable.

The reaction temperature is ordinarily -10° to 180° C., preferably 0° C.to a reflux temperature.

The reaction time is ordinarily 1 to 72 hours, preferably 2 to 48 hours.

(G): Production of the compound (6) from the compound (5)

Ordinarily, a halogenating agent of 0.5 to 5.0 mol, preferably 0.8 to1.5 mol based on the compound (5) is used.

As the halogenating agent, halogens such as chlorine and bromine,hydrogen chloride, sulfuryl chloride, N-chlorosuccineimide,N-bromosuccineimide, N-chloroisocyanuric acid, cuprous bromide andantimony pentachloride are usable.

A solvent is ordinarily necessary for the reaction. As the solvent,organic acids such as formic acid and acetic acid; aliphatichydrocarbons such as hexane, heptane, ligroin and petroleum ether;aromatic hydrocarbons such as benzene, toluene, xylene andchlorobenzene; halogenated hydrocarbons such as chloroform and methylenechloride; ethers such as diethyl ether, dioxane and tetrahydrofuran;sulfolane; water; and a mixture thereof may be exemplified. Among these,the organic acids, ethers, water and a mixture thereof are preferable.

The reaction temperature is ordinarily 0° to 200° C., preferably 10° to130° C.

The reaction time is ordinarily 0.5 to 24 hours, preferably 1 to 12hours.

The thus-obtained sulfoneamide derivative (6) is used as an intermediatefor producing a 6-haloalkyl-3-phenyluracil derivative which is useful asa herbicide, as is seen from the later-described reference examples.

The diamine derivative (2), the nitrocarbalinide derivative (3), theaminocarbanilide derivative (4) and the anilide derivative (5) are alsouseful for an intermediate for producing the sulfoneamide derivative(6).

[EXAMPLES]

Intermediates and a process for producing the same according to thepresent invention will be explained in more detail with reference to thefollowing examples and a process for producing a herbicide by using theintermediate of the present invention will be explained with referenceto the following reference examples. It is to be understood, however,that the present invention is not restricted thereto.

Example 1 Synthesis of N-(4-fluoro-3-nitrophenyl)ethanesulfonamide##STR34##

20.2 g (0.129 mol) of 4-fluoro-3-nitroaniline was dissolved in 120 ml ofpyridine, and 17.8 g (0.136 mol) of ethanesulfonyl chloride was addeddropwise to the solution at a temperature of not higher than 5° C.Thereafter the temperature was raised to room temperature and thereaction was continued for one night. After the pyridine was distilledoff, the thus-obtained product was dissolved in ethyl acetate and washedwith diluted hydrochloric acid twice, then with water, and withsaturated saline solution. The solution was dried over anhydrous sodiumsulfate, and the ethyl acetate was distilled off to obtain the crudeproduct (crystals). The crude product was washed with diisopropyl ether,thereby obtaining 29.7 g of the objective product (yield: 93%) in theform of brown crystals. Melting point: 133° to 136° C.

¹ H-NMR (d₆ -DMSO): δ1.36 (3H, t, J=7 Hz), 3.16 (2H, q, J =7 Hz), 7.31(1H, dd, J=10 Hz), 7.63 (1H, ddd, J=2, 7, 10 Hz), 8.07 (1H, dd, J=2, 7Hz), 10.66 (1H, br s)

Example 2 Synthesis of N-(3-amino-4-fluorophenyl)ethanesulfonamide##STR35##

A mixture of 63.1 g (1.13 mol) of iron powder and 120 ml of an aqueoussolution of 5% acetic acid was heated to 80° C., and a mixed solution of28.0 g (0.113 mol) of N-(4-fluoro-3-nitrophenyl)ethanesulfonamide, 116ml of acetic acid and 116 ml of ethyl acetate was slowly added dropwiseto the resultant mixture. After the reaction was continued for 3 hours,the insolubles were filtered out and washed with ethyl acetate.Thereafter the filtrate was distilled to remove the solvent, and theproduct was dissolved in ethyl acetate and washed with saturated sodiumhydrogencarbonate, water and saturated saline solution. The solution wasdried over anhydrous sodium sulfate, and the ethyl acetate was distilledoff to obtain the crude product (crystals). The crude product was washedwith diisopropyl ether, thereby obtaining 22.0 g of the objectiveproduct (yield: 89%) in the form of light yellow crystals.

Melting point: 106° to 108° C.

¹ H-NMR (d₆ -DMSO): δ1.28 (3H, t, J=7 Hz), 3.05 (2H, q, J=7 Hz), 4.40(2H, br s), 6.48 (1H, ddd, J=2, 7, 10 Hz), 6.77 (1H, dd, J=2, 7 Hz),6.89 (1H, dd, J=10 Hz)

Example 3 Synthesis of ethyl 5-ethylsulfonylamino-2-fluorocarbonilate

(Process a) ##STR36##

10.0 g (50.5 mmol) of ethyl 5-amino-2-fluorcarbanilate was dissolved in60 ml of pyridine, and 6.82 g (53.0 mmol) of ethanesulfonyl chloride wasadded dropwise to the solution at a temperature of not higher than 5° C.Thereafter the temperature was raised to room temperature and thereaction was continued for one night. After the pyridine was distilledoff, the thus-obtained product was dissolved in ethyl acetate and washedwith diluted hydrochloric acid twice, then with water, and withsaturated saline solution. The solution was dried over anhydrous sodiumsulfate, and the ethyl acetate was distilled off to obtain the crudeproduct (crystals). The crude product was recrystallized from ethylacetate-diisopropyl ether, thereby obtaining 9.74 g of the objectiveproduct (yield: 67%) in the form of white crystals.

(Process b) ##STR37##

10.7 g (98.2 mmol) of ethyl chloroformate was added dropwise to amixture of 21.4 g (98.2 mmol) ofN-(3-amino-4-fluorophenyl)ethanesulfonamide, 7.76 g (98.2 mmol) ofpyridine and 214 ml of dichloromethane at a temperature of not higherthan 5° C. Thereafter the temperature was raised to room temperature andthe reaction was continued for 5 hours. After the dichloromethane layerwas separated out by adding water to the reaction mixture, thedichloromethane layer was washed with saturated saline solution anddried over anhydrous sodium sulfate. Thereafter the dichloromethane wasdistilled off to obtain the crude product (crystals). The crude productwas washed with diisopropyl ether, thereby obtaining 28.0 g of theobjective product (yield: 98%) in the form of white crystals. Meltingpoint: 107° to 110° C.

¹ H-NMR (d₆ -DMSO): δ 1.30 (6H, t, J=7 Hz), 3.06 (2H, q, J=7 Hz), 4.22(1H, q, J=7 Hz), 7.00 (2H, br d, J=8 Hz), 7.94 (1H, br d, J=7 Hz), 8.19(1H, br s), 10.41 (1H, br s)

Example 4 Synthesis of ethyl 2-fluoro-5-nitrocarbanilate ##STR38##

10.7 g (98.9 mmol) of ethyl chloroformate was added dropwise to amixture of 15.0 g (94.2 mmol) of 2-fluoro-5-nitroaniline, 8.20 g (104mmol) of pyridine and 150 ml of dichloromethane at a temperature of nothigher than 5° C. Thereafter the temperature was raised to roomtemperature and the reaction was continued for one night. After thedichloromethane layer was separated out by adding water to the reactionmixture, the dichloromethane layer was washed with saturated salinesolution and dried over anhydrous sodium sulfate. Thereafter thedichloromethane was distilled off to obtain the crude product(crystals). The crude product was washed with hexane, thereby obtaining21.1 g of the objective product (yield: 98%) in the form of ochercrystals.

Melting point: 90° to 92° C.

1H-NMR (CDCl₃): δ 1.34 (3H, t, J=7 Hz), 4.30 (2H, q, J=7 Hz), 7.22 (1H,br, s), 7.22 (1H, t, J=9 Hz), 7.91 (1H, ddd, J=3, 6, 9 Hz), 9.03 (1H,dd, J=3, 6 Hz)

Example 5 Synthesis of ethyl 5-amino-2-fluorocarbanilate ##STR39##

A mixture of 39.4 g (706 mmol) of iron powder and 75 ml of an aqueoussolution of 5% acetic acid was heated to 80° C., and a mixed solution of16.1 g (70.6 mmol) of ethyl 2-fluoro-5-nitrocarbanilate, 72 ml of aceticacid and 72 ml of ethyl acetate was slowly added dropwise to themixture. After the reaction was continued for 3 hours, the insolubleswere filtered out and washed with ethyl acetate. Thereafter the filtratewas distilled to remove the solvent, and the resultant product wasdissolved in ethyl acetate and washed with saturated sodiumhydrogencarbonate, water and saturated saline solution. The solution wasdried over anhydrous sodium sulfate, and the ethyl acetate was distilledoff to obtain the crude product (crystals). The crude product was washedwith diisopropyl ether, thereby obtaining 12.8 g of the objectiveproduct (yield: 91%) in the form of light yellow crystals.

Melting point: 88° to 89° C.

¹ H-NMR (CDCl₃): δ1.24 (3H, t, J=7 Hz), 3.78 (2H, br s), 4.19 (2H, q,J=7 Hz), 6.23 (1H, ddd, J=2, 7, 10 Hz), 6.80 (1H, dd, J=10 Hz), 7.23(1H, br s), 7.44 (1H, dd, J=2, 7 Hz)

Example 6 Synthesis of ethyl4-chloro-5-ethylsulfonylamino-2-fluorocabanilate

(Process a) ##STR40##

1.00 g (3.45 mmol) of ethyl 5-ethylsulfonylamino-2-fluorocarbanilate wasdissolved in 10 ml of acetic acid, and chlorine gas was added to theresultant solution at a temperature of not higher than 25° C. until thestarting material disappeared. After the reaction was completed, thesurplus chlorine gas was removed by blowing nitrogen gas thereinto, anddiisopropyl ether was added. The precipitated crystals were filtered outto obtain 0.76 g of the objective product (yield: 68%) in the form ofwhite crystals.

(Process b) ##STR41##

0.50 g (1.72 mmol) of ethyl 5-ethylsulfonylamino-2-fluorocarbanilate wasadded to 4 ml of sulfuryl chloride. The sulfuryl chloride was distilledoff after 10 minutes, and the resultant product was dissolved in ethylacetate. The solution was washed with water and a saturated salinesolution, and dried over anhydrous sodium sulfate. The ethyl acetate wasdistilled off to obtain the crude product. The crude product was washedwith diisopropyl ether, thereby obtaining 0.21 g of the objectiveproduct (yield: 38%) in the form of white crystals.

(Process c) ##STR42##

0.50 g (1.72 mmol) of ethyl 5-ethylsulfonylamino-2-fluorocarbanilate wasdissolved in a mixed solution of 12 ml of acetic acid and 1 ml of water,and chlorine gas was added to the resultant solution at a temperature ofnot higher than 25° C. until the starting material disappeared. Afterthe reaction was completed, the surplus chlorine gas was removed byblowing nitrogen gas thereinto, and water was added. The precipitatedcrystals were filtered out and dried to obtain 0.49 g of the objectiveproduct (yield: 88%) in the form of white crystals.

Melting point: 162° to 164° C.

¹ H-NMR (d₆ -DMSO): δ1.28 (3H, t, J=7 Hz), 1.32 (3H, t, J=7 Hz), 3.08(2H, q, J=7 Hz), 4.12 (2H, q, J=7 Hz), 7.13 (1H, d, J=9 Hz), 7.88 (1H,d, J=7 Hz), 8.88 (1H, br s), 8.94 (1H, br s)

Example 7 Synthesis of N-(3-amino-4-fluorophenyl)ethanesulfonamide##STR43##

50.4 mg (5 wt %) of platinum oxide (Adams catalyst) was added to amixture of 1.00 g (4.03 mmol) ofN-(4-fluoro-3-nitrophenyl)ethanesulfoneamide and 40 ml of ethanol, andthe resultant mixture was stirred until 285 ml of hydrogen was absorbed.The reaction mixture was filtered through a glass filter to remove thecatalyst, and the solvent was then distilled off under a reducedpressure. Thus, 850 mg of the objective product (yield: 97%) wasobtained in the form of light brown crystals.

Example 8 Synthesis of methyl 5-ethylsulfonylamino-2-fluorocarbanilate##STR44##

22.1 g (229 mmol) of methyl chloroformate was added dropwise to amixture of 50.0 g (229 mmol) ofN-(3-amino-4-fluorophenyl)ethanesulfonamide, 18.1 g (229 mmol) ofpyridine and 500 ml of dichloromethane at a temperature of not higherthan 5° C. Thereafter the temperature was raised to room temperature andthe reaction was continued for 5 hours. After the dichloromethane layerwas separated out by adding water to the resultant mixture, thedichloromethane layer was washed with saturated saline solution anddried over anhydrous sodium sulfate. Thereafter the dichloromethane wasdistilled off to obtain the crude product (crystals). The crude productwas washed with diisopropyl ether, thereby obtaining 61.0 g of theobjective product (yield: 96%) in the form of light brown crystals.

Example 9 Synthesis of ethyl 5-amino-2-fluorocarbanilate ##STR45##

100.3 mg (10 wt %) of 5% palladium carbon (containing water) was addedto a mixture of 1.00 g (4.39 mmol) of ethyl 2-fluoro-5-nitrocarbanilateand 20 ml of ethanol, and the resultant mixture was stirred until 309 mlof hydrogen was absorbed. The reaction mixture was filtered to removethe catalyst, and the solvent was then distilled off under a reducedpressure. Thus, 700 mg of the objective product (yield: 81%) wasobtained in the form of light brown crystals.

Example 10 Synthesis of ethyl 5-methylsulfonylamino-2-fluorocarbanilate##STR46##

61.1 g (533 mmol) of methanesulfonyl chloride was added dropwise to amixture of 96.0 g (485 mmol) of ethyl 5-amino-2-fluorocarbanilate, 46.0g (582 mmol) of pyridine and 700 ml of dichloromethane at a temperatureof not higher than 5° C. Thereafter the temperature was raised to roomtemperature and the reaction was continued for one night. After thesolvent was distilled off, the resultant product was dissolved in ethylacetate and washed with diluted hydrochloric acid twice, then withwater, and with saturated saline solution. The resultant solution wasdried over anhydrous sodium sulfate, and the ethyl acetate was distilledoff to obtain the crude procut (crystals). The crude product was washedwith diisopropyl ether, thereby obtaining 126 g of the objective product(yield: 94%) in the form of light brown crystals.

Example 11 Synthesis of ethyl4-chloro-5-ethylsulfonylamino-2-fluorocarbanilate ##STR47##

0.50 g (1.72 mmol) of ethyl 5-ethylsulfonylamino-2-fluorocarbanilate wasdissolved in a mixture of 5 ml of dioxane and 1 ml of water, andchlorine gas was added to the resultant solution at a temperature of nothigher than 25° C. until the starting material disappeared. After thereaction was completed, the surplus chlorine gas was removed by blowingnitrogen gas thereinto, and water was added. The precipitates crystalswere filtered out and dried to obtain 0.48 g of the objective product(yield: 86%) in the form of light brown crystals.

Example 12 Synthesis of ethyl4-chloro-5-methylsulfonylamino-2-fluorocarbanilate ##STR48##

80.6 g (292 mmol) of ethyl 5-methylsulfonylamino-2-fluorocarbanilate wasdissolved in a mixture of 1075 ml of acetic acid and 100 ml of water,and chlorine gas was added to the resultant solution at a temperature ofnot higher than 25° C. until the starting material disappeared. Afterthe reaction was completed, the surplus chlorine gas was removed byblowing nitrogen gas thereinto, and hexane was added. The precipitatescrystals were filtered out to obtain 81.4 g of the objective product(yield: 90%) in the form of yellow crystals.

Reference Example 1 Synthesis of3-(4-chloro-5-ethylsulfonylamino-2-fluorophenyl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione##STR49##

1.06 g (5.77 mmol) of ethyl 3-amino-4,4,4-trifluorocrotonate wasdissolved in 6.2 ml of N,N-dimethylformamide and 0.82 g (14.4 mmol) ofsodium methoxide was added thereto. The reaction mixture was cooled tonot higher than 5° C. after 10 minutes, and 1.56 g (4.81 mmol) of ethyl4-chloro-5-ethylsulfonylamino-2-fluorocarbanilate was added thereto. Theresultant mixture was heated to 110° C. and reacted for 4 hours. Afterthe reaction was completed, N,N-dimethylformamide was distilled off andthe resultant product was dissolved in water. The thus-obtained solutionwas washed with diethyl ether 3 times and thereafter concentratedhydrochloric acid was added thereto to pH 2. The precipitated crystalswere filtered out, washed with water and dried to obtain 1.54 g of theobjective product (yield: 77%) in the form of light yellow crystals.

Melting point: 190° to 192° C.

¹ H-NMR (d₆ -DMSO): δ1.36 (3H, t, J=7 Hz), 3.12 (2H, q, J=7 Hz), 6.19(1H, s), 7.44 (1H, d, J=9 Hz), 7.58 (1H, d, J=7 Hz), 8.86 (1H, br s),9.20 (1H, br s)

Reference Example 2 Synthesis of3-(4-chloro-5-ethylsulfonylamino-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione##STR50##

1.00 g (2.41 mmol) of3-(4-chloro-5-ethylsulfonylamino-2-fluorophenyl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedionewas dissolved in 10 ml of acetone, and 0.17 g (1.20 mmol) of anhydrouspotassium carbonate and 0.23 ml (2.41 mmol) of dimethyl sulfate wereadded thereto and the reaction was continued for 1.5 hours. Afteracetone was distilled off, the reaction product was dissolved in ethylacetate, washed with water and saturated saline solution, and dried overanhydrous sodium sulfate. Thereafter the ethyl acetate was distilled offto obtain a crude product. The crude product was recrystallized fromchloroformdiethyl ether, thereby obtaining 0.61 g of the objectiveproduct (yield: 59%) in the form of light yellow crystals.

Melting point: 176° to 177° C.

¹ H-NMR (d₆ -DMSO): δ1.32 (3H, t, J=7 Hz), 3.06 (2H, q, J=7 Hz), 3.43(3H, s), 6.23 (1H, s), 7.29 (1H, d, J=9 Hz), 7.41 (1H, d, J=7 Hz), 9.11(1H, br s)

Reference Example 3 Test of herbicidal effect of soil treatment

50 parts of3-(4-chloro-5-ethylsulfonylamino-2-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4-(1H,3H)pyrimidinedione,47 parts of Zeeklite (Kaolin clay, produced by Zeeklite MiningIndustries Co., Ltd.), 2 parts of Sorpol 5039 (anionic surfactant,produced by Toho Chemical Ind. Co., Ltd.) and 1 part of Carplex (whitecarbon, produced by Shionogi Co., Ltd.) were uniformly mixed andpulverized to produce a wettable powder.

Sterilized diluvial soil was placed into a plastic box [15 cm(long)×22cm(wide)×6 cm(deep)], and sowed at random with the seeds of Echinochloacrus-qalli, Digitaria adscendens, Cyperus microiria, Solanum nigrum,Galinsoga ciliata, Rorippa indica, rice, corn, wheat, soybean andcotton. The diluvial soil was then covered with soil to a depth of about1 cm, and the wettable powder diluted with water was uniformly sprayedonto the surface of the soil at a predetermined rate. The herbicidaleffect on the respective grasses was examined after 3 weeks inaccordance with the following evaluation criteria:

Standard ratings:

5: Growth control rate of more than 90% (almost completely withered)

4: Growth control rate of from 70 to 90%

3: Growth control rate of from 40 to 70%

2: Growth control rate of from 20 to 40%

1: Growth control rate of from 5 to 20%

0: Growth control rate of less than 5% (almost non-effective)

The above growth control rates were calculated by the followingequation:

    Growth control rate (%)=(1-T/N)×100

where

T: weight of the weed growth above the soil surface of the treated area,

N: weight of the weed grown above the soil surface of the non-treatedarea.

In Table 1, the respective symbols represent the following grasses.

N (Echinochloa crus-qalli), M (Digitaria adscendens), K (Cyperusmicroiria), H (Solanum nilrum), D (Galinsoga ciliata), I (Rorippaindica), R (rice), T (corn), W (wheat), S (soybean) and C (cotton)

                  TABLE 1                                                         ______________________________________                                        Dosage                                                                        (g/ha)                                                                              N     M     K    H   D    I   R    T   W    S   C                       ______________________________________                                        10    5     3     5    5   5    5   0    0   0    0   2                       20    5     4     5    5   5    5   1    0   0    0   4                       40    5     5     5    5   5    5   3    0   0    0   5                       ______________________________________                                    

What is claimed is:
 1. A process for producing a sulfonamide derivativerepresented by the following formula (6): ##STR51## (wherein X and Yindependently represent a halogen atom, R represents a C₁ -C₄ alkylgroup or a C₁ -C₃ haloalkyl group and R' represents a C₁ -C₄ alkyl groupor a phenyl group), comprising the steps of:reacting4-halogeno-3-nitroaniline represented by the following general formula(9): ##STR52## with an alkylsulfonyl halide represented by the followinggeneral formula (11):

    Hal--SO.sub.2 R                                            (11)

(wherein Hal represents a halogen atom)so as to obtain a nitroanilinederivative represented by the following general formula (1): ##STR53##reducing the nitroaniline derivative represented by the formula (1) soas to obtain a diamine derivative represented by the following generalformula (2): ##STR54## reacting the diamine derivative represented bythe formula (2) with a halogenoformate represented by the followinggeneral formula (12):

    Hal--CO.sub.2 R'                                           (12)

so as to obtain an anilide derivative represented by the followinggeneral formula (5): ##STR55## halogenating the anilide derivativerepresented by the formula (5).
 2. A process for producing a sulfonamidederivative represented by the following formula (6): ##STR56## (whereinX and Y independently represent a halogen atom, R represents a C₁ -C₄alkyl group or a C₁ -C₃ haloalkyl group and R' represents a C₁ -C₄ alkylgroup or a phenyl group), comprising the steps of:reacting2-halogeno-5-nitroaniline represented by the following general formula(10): ##STR57## with a halogenoformate represented by the followinggeneral formula (12):

    Hal--CO.sub.2 R'                                           (12)

(wherein Hal represents a halogen atom)so as to obtain anitrocarbanilide derivative represented by the following general formula(3): ##STR58## reducing the nitrocarbanilide derivative represented bythe formula (3) so as to obtain an aminocarbanilide derivativerepresented by the following general formula (4): ##STR59## reacting theaminocarbanilide derivative represented by the general formula (4) withan alkylsulfonyl halide represented by the following general formula(11):

    Hal--SO.sub.2 R                                            (11)

so as to obtain an anilide derivative represented by the followinggeneral formula (5): ##STR60## halogenating the anilide derivativerepresented by the formula (5).
 3. A process for producing a sulfonamidederivative represented by formula (6): ##STR61## wherein X and Yindependently represent a halogen atom, R represents a C₁ -C₄ alkylgroup or a C₁ -C₃ haloalkyl group and R' represents a C₁ -C₄ alkyl groupor a phenyl group, comprising the step of halogenating an anilidederivative represented by formula (5): ##STR62##
 4. The process of claim3, wherein the anilide derivative of formula (5): ##STR63## wherein Xrepresents a halogen atom, R represents a C₁ -C₄ alkyl group or a C₁ -C₃haloalkyl group and R' represents a C₁ -C₄ alkyl group or a phenylgroup, is produced by reacting a diamine derivative represented byformula (2): ##STR64## with a halogenoformate represented by formula(12):

    Hal--CO.sub.2 R'                                           (12)

wherein Hal represents a halogen atom.
 5. The process of claim 4 whereinthe diamine derivative of formula (2): ##STR65## wherein X represented ahalogen atom and R represents a C₁ -C₄ alkyl group or a C₁ -C₃ haloalkylgroup is prepared by reducing a nitroaniline derivative represented byformula (1): ##STR66##
 6. The process of claim 5, wherein thenitroaniline derivative of formula (1): ##STR67## wherein X represents ahalogen atom and R represents a C₁ -C₄ alkyl group of a C₁ -C₃ haloalkylgroup is prepared by reacting 4-halogeno-3-nitroaniline represented byformula (9): ##STR68## with an alkylsulfonyl halide represented byformula (11):

    Hal--SO.sub.2 R                                            (11)

wherein Hal represents a halogen atom.
 7. The process of claim 3,wherein the anilide derivatives of formula (5): ##STR69## wherein Xrepresents a halogen atom, R represents a C₁ -C₄ alkyl group of a C₁ -C₃haloalkyl group and R' represents a C₁ -C₄ alkyl group or a phenyl groupis produced by reacting an aminocarbanilide derivative represented byformula (4): ##STR70## with an alkylsulfonyl halide represented byformula (11):

    Hal--SO.sub.2 R                                            (11)

wherein Hal represents a halogen atom.
 8. The process of claim 7,wherein the aminocarbanilide derivative represented by formula (4):##STR71## wherein X represents a halogen atom and R' represents a C₁ -C₄alkyl group or a phenyl group is produced by reducing a nitrocarbanilidederivative represented by formula (3): ##STR72## wherein X is as definedabove.
 9. The process of claim 8, wherein the nitrocarbanilidederivative represented by formula (3): ##STR73## wherein X represents ahalogen atom and R' represents a C₁ -C₄ alkyl group or a phenyl group isproduced by reacting 2-halogen-5-nitroaniline represented by formula(10): ##STR74## with a halogenoformate represented by formula (12):

    Hal--CO.sub.2 R'                                           (12)

wherein Hal represents a halogen atom.